JPWO2018181496A1 - Composition for forming release layer and release layer - Google Patents

Abstract

Provided is a composition for forming a release layer, comprising a polyamic acid having a weight average molecular weight of 5,000 or more containing a structural unit represented by the formula (1) and an organic solvent. [Wherein, X1 represents a phenyl group or a biphenyl group, Z1 is a group represented by the following formula [Z1], and n1 represents a natural number.) (In the formula [Z1], Y1 is a single bond. Or a bonding group, Y2 represents a single bond, an alkylene group having 1 to 15 carbon atoms, Y3 represents a single bond or an alkylene group having 1 to 15 carbon atoms, and Y4 represents a single bond, a cyclic group, or a steroid. A divalent organic group having a skeleton, Y5 represents a divalent cyclic group such as a benzene ring or the like; n represents an integer of 0 to 4; Y6 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and the bonding group represents -O- or the like.]

Description

  The present invention relates to a composition for forming a release layer and a release layer.

2. Description of the Related Art In recent years, electronic devices have been required to have functions such as bending and thinning and lightening. For this reason, it is required to use a lightweight flexible plastic substrate instead of the conventional heavy and fragile glass substrate which cannot be bent.
In particular, for a new generation display, development of an active matrix type full-color TFT display panel using a lightweight flexible plastic substrate (hereinafter, referred to as a resin substrate) is required. The technology relating to this new generation display is expected to be applied to various fields such as a flexible display, a flexible smartphone, and a mirror display.

  Therefore, various methods for manufacturing an electronic device using a resin film as a substrate have begun to be studied, and for a new generation display, a manufacturing study is being conducted by a process that can use existing TFT equipment. For example, in Patent Documents 1, 2, and 3, after forming an amorphous silicon thin film layer on a glass substrate, forming a plastic substrate on the thin film layer, irradiating a laser from the glass surface side to crystallize the amorphous silicon. Discloses a method of separating a plastic substrate from a glass substrate by using hydrogen gas generated as a result.

  In Patent Document 4, a method of completing a liquid crystal display device by attaching a layer to be peeled (described as “transferred layer” in Patent Document 4) to a plastic film using the technology disclosed in Patent Documents 1 to 3 is described. Is disclosed.

  However, in the methods disclosed in Patent Literatures 1 to 4, particularly in the method disclosed in Patent Literature 4, it is essential to use a substrate having high translucency in order to transmit a laser beam. In addition, it is necessary to irradiate a laser beam of relatively large energy enough to release hydrogen contained in the amorphous silicon, and the laser beam irradiation may damage the layer to be peeled. That is the problem. In addition, when the release layer has a large area, it takes a long time for the laser treatment, and it is difficult to increase the productivity of device fabrication.

JP-A-10-125929 JP-A-10-125931 International Publication No. 2005/050754 JP-A-10-125930

  The present invention has been made in view of the above circumstances, a composition for forming a release layer for forming a release layer that can be peeled without damaging the resin substrate of the flexible electronic device, and the release layer The purpose is to provide.

  The present inventors have conducted intensive studies to solve the above problems, and as a result, in the production of a resin substrate, a release layer formed on a substrate, a release layer containing a polyamic acid having a specific structure, and an organic solvent By forming using the forming composition, it is possible to obtain a release layer having excellent adhesion to a substrate and appropriate adhesion to a resin substrate used as a flexible electronic device and appropriate release properties. Heading, the present invention has been completed.

［（式中、Ｘ¹は、フェニル基又はビフェニル基を表し、Ｚ¹は、下記式［Ｚ１］で表される基であり、ｎ¹は自然数を表す。）

（式［Ｚ１］中、
Ｙ¹は、単結合又は結合基を表し、
Ｙ²は、単結合、炭素数１〜１５のアルキレン基若しくは−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−を表すか、又はベンゼン環、シクロヘキサン環及び複素環からなる群から選ばれる２価の環状基を表し、上記環状基上の任意の水素原子が、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基、炭素数１〜３のフッ化アルキル基、炭素数１〜３のフッ化アルコキシ基又はフッ素原子で置換されていてもよく、
Ｙ³は、単結合又は炭素数１〜１５のアルキレン基を表し、
Ｙ⁴は、単結合を表すか、又はベンゼン環、シクロヘキサン環及び複素環からなる群から選ばれる２価の環状基、又は炭素数１７〜３０のステロイド骨格を有する２価の有機基を表し、上記環状基上の任意の水素原子が、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基、炭素数１〜３のフッ化アルキル基、炭素数１〜３のフッ化アルコキシ基又はフッ素原子で置換されていてもよく、
Ｙ⁵は、ベンゼン環、シクロヘキサン環及び複素環からなる群から選ばれる２価の環状基を表し、これらの環状基上の任意の水素原子が、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基、炭素数１〜３のフッ化アルキル基、炭素数１〜３のフッ化アルコキシ基又はフッ素原子で置換されていてもよく、
ｎは０〜４の整数を表し、ｎが２以上の場合、Ｙ⁵同士は同一でも異なっていてもよく、
Ｙ⁶は、水素原子、炭素数１〜１８のアルキル基、炭素数１〜１８のフッ化アルキル基、炭素数１〜１８のアルコキシ基又は炭素数１〜１８のフッ化アルコキシ基を表し、
Ｙ²及びＹ³におけるアルキレン基、並びに、上記環状基上の置換基又はＹ⁶におけるアルキル基、フッ化アルキル基、アルコキシ基及びフッ素含有アルコキシ基は、直鎖状、枝分かれ状、若しくは環状の何れか又はそれらの組み合わせであってもよく、
またＹ²及びＹ³におけるアルキレン基、並びに、Ｙ⁶におけるアルキル基、フッ化アルキル基、アルコキシ基及びフッ素含有アルコキシ基は、結合基同士が隣り合わない限り１〜３の結合基で中断されていてもよく、
さらにＹ²、Ｙ⁴若しくはＹ⁵が２価の環状基を表すか、又はＹ⁴がステロイド骨格を有する２価の有機基を表すか、又はＹ²が−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−を表すか、又はＹ²若しくはＹ³がアルキレン基を表すか、又はＹ⁶がアルキル基若しくはフッ化アルキル基を表すとき、該２価の環状基、該ステロイド骨格を有する２価の有機基、該−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−、該アルキレン基、該アルキル基及び該フッ化アルキル基は、それらに隣接する基と結合基を介して結合していてもよく、
そして上記結合基は、−Ｏ−、−ＣＨ₂Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨ−、−ＮＨＣＯ−、−ＮＨ−ＣＯ−Ｏ−及び−ＮＨ−ＣＯ−ＮＨ−からなる群から選ばれる基を表し、
但し、Ｙ²〜Ｙ⁶がそれぞれ表すところの単結合、炭素数１〜１５のアルキレン基、ベンゼン環、シクロヘキサン環、複素環、ステロイド骨格を有する２価の有機基、−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−、炭素数１〜１８のアルキル基、炭素数１〜１８のフッ化アルキル基、炭素数１〜１８のアルコキシ基及び炭素数１〜１８のフッ化アルコキシ基の炭素数の合計は６〜３０である。）］
２． 上記Ｚ¹が、下記式［Ｚ２］で表される基である１の剥離層形成用組成物、

（式中、Ｙ¹は、単結合、−Ｏ−又は−ＮＨ−を表し、
Ｙ⁵は、ベンゼン環及びシクロヘキサン環からなる群から選ばれる２価の環状基を表し、
ｎは１〜３の整数を表し、ｎが２以上の場合、Ｙ⁵同士は同一でも異なっていてもよく、
Ｙ⁶は、炭素数１〜１８のアルキル基を表す。）
３． 上記Ｚ¹が、下記式［Ｚ３］、［Ｚ４］又は［Ｚ５］で表される基である２の剥離層形成用組成物、

（式中、Ｙ⁶は、互いに独立して、炭素数１〜１８のアルキル基を表す。）
４． 上記有機溶剤が、式（Ｓ１）で表されるアミド類、式（Ｓ２）で表されるアミド類及び式（Ｓ３）で表されるアミド類から選ばれる少なくとも１つを含む１〜３のいずれかの剥離層形成用組成物、

（式中、Ｒ¹及びＲ²は、互いに独立して、炭素数１〜１０のアルキル基を表し、Ｒ³は、水素原子、又は炭素数１〜１０のアルキル基を表し、ｈは、自然数を表す。）
５． １〜４のいずれかの剥離層形成用組成物を用いて形成される剥離層、
６． １〜４のいずれかの剥離層形成用組成物を基体に塗布し、焼成することを含む剥離層の製造方法、
７． １〜４のいずれかの剥離層形成用組成物を基体上に塗布し、焼成して剥離層を形成する工程、
上記剥離層上に、被剥離体を形成する工程、及び
上記被剥離体を、上記剥離層から剥離する工程
を含む被剥離体の製造方法、
８． ５の剥離層を用いることを特徴とする、樹脂基板を備えるフレキシブル電子デバイスの製造方法、
９． ５の剥離層を用いることを特徴とする、樹脂基板を備えるタッチパネルセンサーの製造方法、
１０． 上記樹脂基板が、ポリイミド樹脂基板である７又は８の製造方法、
１１． フレキシブル電子デバイスに適用される積層体であって、
基体と、
上記基体上に形成される剥離層と、
上記剥離層上に形成される樹脂基板と
を有し、上記剥離層が１〜４のいずれかの剥離層形成用組成物により形成され、かつ、上記樹脂基板と上記剥離層との密着力が、上記剥離層と上記基体との密着力より大きいことを特徴とする積層体
を提供する。That is, the present invention
1. A release layer-forming composition comprising a polyamic acid having a weight average molecular weight of 5,000 or more containing a structural unit represented by the following formula (1) and an organic solvent:

[Wherein, X ¹ represents a phenyl group or a biphenyl group, Z ¹ is a group represented by the following formula [Z1], and n ¹ represents a natural number.)

(In the formula [Z1],
Y ¹ represents a single bond or a bonding group,
Y ² represents a single bond, an alkylene group having 1 to 15 carbon atoms or —CH ₂ —CH (OH) —CH ₂ —, or a divalent group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. Represents a cyclic group, and any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, May be substituted with a fluorinated alkoxy group or a fluorine atom,
Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms,
Y ⁴ represents a single bond or a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a steroid skeleton having 17 to 30 carbon atoms, Any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxy group having 1 to 3 carbon atoms Or may be substituted with a fluorine atom,
Y ⁵ represents a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, May be substituted with an alkoxy group having 1 to 3, a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxy group having 1 to 3 carbon atoms or a fluorine atom,
n represents an integer of 0 to 4, when n is 2 or more, Y ⁵ together may be the same or different,
Y ⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorinated alkoxy group having 1 to 18 carbon atoms,
The alkylene group in Y ² and Y ^3, and the substituent on the cyclic group or the alkyl group, fluorinated alkyl group, alkoxy group and fluorine-containing alkoxy group in Y ⁶ may be any of linear, branched, or cyclic. Or a combination thereof,
The alkylene group in Y ² and Y ³ and the alkyl group, fluorinated alkyl group, alkoxy group and fluorine-containing alkoxy group in Y ⁶ are interrupted by 1 to 3 bonding groups unless the bonding groups are adjacent to each other. May be
Further, Y ² , Y ⁴ or Y ⁵ represents a divalent cyclic group, Y ⁴ represents a divalent organic group having a steroid skeleton, or Y ² represents —CH ₂ —CH (OH) —CH _{When 2-} represents, or Y ² or Y ³ represents an alkylene group, or Y ⁶ represents an alkyl group or a fluorinated alkyl group, the divalent cyclic group or the divalent organic having the steroid skeleton group, the _{-CH 2 -CH (OH) -CH 2} -, the alkylene group, the alkyl group and the fluorinated alkyl group may be bonded through a bonding group and groups adjacent to them,
The bonding group is a group consisting of —O—, —CH ₂ O—, —COO—, —OCO—, —NH—, —NHCO—, —NH—CO—O—, and —NH—CO—NH—. Represents a group selected from
However, a single bond represented by each of Y ^{2 to} Y ^6, an alkylene group having 1 to 15 carbon atoms, a benzene ring, a cyclohexane ring, a heterocyclic ring, a divalent organic group having a steroid skeleton, —CH ₂ —CH (OH ) —CH ₂ —, the total number of carbon atoms of an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a fluorinated alkoxy group having 1 to 18 carbon atoms Is 6 to 30. )]
2. 1. The composition for forming a release layer according to ¹ , wherein Z ¹ is a group represented by the following formula [Z2],

(Wherein, Y ¹ represents a single bond, —O— or —NH—,
Y ⁵ represents a divalent cyclic group selected from the group consisting of a benzene ring and a cyclohexane ring,
n represents an integer of 1 to 3, when n is 2 or more, Y ⁵ together may be the same or different,
Y ⁶ represents an alkyl group having 1 to 18 carbon atoms. )
3. 2. The composition for forming a release layer according to 2, wherein Z ¹ is a group represented by the following formula [Z3], [Z4] or [Z5],

(In the formula, Y ⁶ independently represents an alkyl group having 1 to 18 carbon atoms.)
4. Any one of the above 1 to 3, wherein the organic solvent contains at least one selected from the amides represented by the formula (S1), the amides represented by the formula (S2), and the amides represented by the formula (S3) A composition for forming a release layer,

(Wherein, R ¹ and R ² independently represent an alkyl group having 1 to 10 carbon atoms, R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and h is a natural number. Represents.)
5. A release layer formed using the composition for forming a release layer according to any one of 1 to 4,
6. A method for producing a release layer, comprising applying the composition for forming a release layer according to any one of 1 to 4 to a substrate, and firing the composition.
7. A step of applying a release layer-forming composition according to any one of 1 to 4 on a substrate and baking to form a release layer;
A step of forming a body to be peeled on the peeling layer, and a method of manufacturing a body to be peeled including a step of peeling the body to be peeled from the peeling layer;
8. 5. A method for manufacturing a flexible electronic device including a resin substrate, comprising using the release layer of (5).
9. 5. A method for manufacturing a touch panel sensor including a resin substrate, wherein
10. The method according to 7 or 8, wherein the resin substrate is a polyimide resin substrate;
11. A laminate applied to a flexible electronic device,
A substrate;
A release layer formed on the substrate,
A resin substrate formed on the release layer, wherein the release layer is formed of any of the release layer-forming compositions of 1 to 4, and the adhesion between the resin substrate and the release layer is And a laminate having a larger adhesive strength between the release layer and the substrate.

  By using the composition for forming a release layer of the present invention, a release layer having excellent adhesion to a substrate, appropriate adhesion to a resin substrate, and appropriate release properties can be obtained with good reproducibility. By using the composition for forming a release layer according to the present invention, in the process of manufacturing a flexible electronic device, the resin substrate formed on the base and the circuit and the like provided thereon are not damaged without damaging the circuit or the like. In addition, the resin substrate can be separated from the base. Therefore, the composition for forming a release layer of the present invention can contribute to simplification of a manufacturing process of a flexible electronic device having a resin substrate, improvement of the yield, and the like.

Hereinafter, the present invention will be described in more detail.
The composition for forming a release layer according to the present invention contains a polyamic acid having a weight average molecular weight of 5,000 or more containing a structural unit represented by the following formula (1) and an organic solvent.

In the above formula (1), X ¹ represents a phenyl group or a biphenyl group, Z ¹ represents a group represented by the following formula [Z1], and n ¹ represents a natural number.

In the formula [Z1], Y ¹ represents a single bond or a bonding group, Y ² represents a single bond, an alkylene group having 1 to 15 carbon atoms, or —CH ₂ —CH (OH) —CH ₂ —, or Represents a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, wherein any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. May be substituted with a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms, Y ⁴ represents a single bond or a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having 17 to 30 carbon atoms and having a steroid skeleton. , Any hydrogen atom on the above cyclic group May be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxy group having 1 to 3 carbon atoms or a fluorine atom. , Y ⁵ represents a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, May be substituted by an alkoxy group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxy group having 1 to 3 carbon atoms or a fluorine atom, n represents an integer of 0 to 4, and n represents In the case of 2 or more, Y ⁵ may be the same or different, and Y ⁶ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms. Represents a group or a fluorinated alkoxy group having 1 to 18 carbon atoms, The alkylene group in Y ² and Y ^3, and the substituent on the cyclic group or the alkyl group, fluorinated alkyl group, alkoxy group and fluorine-containing alkoxy group in Y ⁶ may be any of linear, branched, or cyclic. Or a combination thereof, and the bonding groups are not adjacent to each other in the alkylene group in Y ² and Y ³ , and the alkyl group, alkyl fluoride group, alkoxy group and fluorine-containing alkoxy group in Y ⁶ As long as Y ² , Y ⁴ or Y ⁵ represents a divalent cyclic group, or Y ⁴ represents a divalent organic group having a steroid skeleton. or Y ² is _{-CH 2 -CH (OH) -CH 2} - Table or if Y ² or Y ³ represents an alkylene group, or Y ⁶ is an alkyl group or fluorinated alkyl group represents an When, the divalent cyclic group, a divalent organic group having the steroid skeleton, the _{-CH 2 -CH (OH) -CH 2} -, the alkylene group, the alkyl group and the fluorinated alkyl group, they well, and the linking _group, -O be bonded via a linking group to the adjacent group -, - CH 2 O -, - COO -, - OCO -, - NH -, - NHCO -, - Represents a group selected from the group consisting of NH—CO—O— and —NH—CO—NH—, provided that a single bond represented by each of Y ^{2 to} Y ^6, an alkylene group having 1 to 15 carbon atoms, and a benzene ring , cyclohexane ring, a heterocyclic ring, a divalent organic group having a steroid _{skeleton, -CH 2 -CH (OH) -CH} 2 -, alkyl group having 1 to 18 carbon atoms, fluorinated alkyl group having 1 to 18 carbon atoms, An alkoxy group having 1 to 18 carbon atoms and a fluorine atom having 1 to 18 carbon atoms The total number of carbon atoms of the alkoxy group is 6 to 30.

  Here, in the present invention, the release layer is a layer provided immediately above a substrate (such as a glass substrate) on which a resin substrate is formed. As a typical example, in a manufacturing process of a flexible electronic device, the resin substrate is fixed between the base and a resin substrate of a flexible electronic device made of a resin such as a polyimide resin or an acrylic resin during a predetermined process. And a release layer provided so that the resin substrate can be easily separated from the base after an electronic circuit or the like is formed on the resin substrate.

The polyamic acid used in the present invention is not particularly limited as long as it has the above-mentioned structure, but is obtained by reacting a diamine component containing a diamine having the following specific structure with a tetracarboxylic dianhydride component. Can be done. That is, a polyamic acid obtained herein are those having Z ¹ in the side chain.

In the present invention, the above Z ¹ indicates a group represented by the following formula [Z1].

In the formula [Z1], Y ¹ represents a single bond or a bonding group. The linking _{group, -O -, - CH 2 O} -, - COO -, - OCO -, - NH -, - NHCO -, - from NHCO-O-and -NH-CO-NH- group consisting Represents a selected group.

In the formula [Z1], Y ² represents a single bond, an alkylene group having 1 to 15 carbon atoms, or —CH ₂ —CH (OH) —CH ₂ —.
Examples of Y ² include a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring. Any hydrogen atom on these cyclic groups may be an alkyl group having 1 to 3 carbon atoms. May be substituted with an alkoxy group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a fluorine atom.

  Examples of the alkylene group having 1 to 15 carbon atoms include a divalent group obtained by removing one hydrogen atom from an alkyl group having 1 to 15 carbon atoms among alkyl groups having 1 to 18 carbon atoms described below. Examples include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene groups and the like.

  Specific examples of the heterocyclic ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring , Pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, cinnoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring and the like. More preferably a pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyrazoline ring, carbazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine , Benzimidazole ring.

  Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a cyclopropyl group. A group in which an oxygen atom -O- is bonded to the group mentioned as a specific example of the alkyl group 3 can be mentioned. The above-mentioned C1-C3 fluorinated alkyl group and C1-C3 fluorinated alkoxy group include any of the above-mentioned C1-C3 alkyl groups and C1-C3 alkoxy groups. Examples thereof include a group in which an atom is substituted with a fluorine atom.

  Among the above-mentioned divalent cyclic groups selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, a divalent cyclic group selected from a benzene ring and a cyclohexane ring is preferred from the viewpoint of ease of synthesis. .

In the formula [Z1], Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms. Examples of the alkylene group having 1 to 15 carbon atoms include the same as those described above.

In the above formula [Z1], Y ⁴ represents a single bond or a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups is It may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxy group having 1 to 3 carbon atoms or a fluorine atom. Examples of the above-mentioned heterocyclic ring and the alkyl group and the like mentioned as the substituent include the same as those described above for Y ² .

Further, Y ⁴ may be a divalent organic group having 17 to 30 carbon atoms and having a steroid skeleton. Preferred examples thereof include cholesteryl, androsteryl, β-cholesteryl, epiandrosteryl, erygosteryl, estolyl, 11α-hydroxymethylsteryl, 11α-progesteryl, lanosteryl, mestranyl, methyltestosterolyl, norethisteryl, pregrenolonyl, β-sitosteryl, It is a divalent organic group having a structure obtained by removing two hydrogen atoms from a structure selected from stigmasteryl, testosteryl, cholesterol acetate, and the like. More specifically, for example, the following divalent organic groups can be mentioned.

（式中、＊は結合位置を表す。）

(In the formula, * represents a bonding position.)

Among these, from the viewpoint of ease of synthesis, Y ⁴ is a divalent cyclic group selected from a benzene ring and a cyclohexane ring, and a divalent organic group having 17 to 30 carbon atoms and having a steroid skeleton. It is preferably a group.

In the formula [Z1], Y ⁵ represents a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms. It may be substituted with a group, a C1-C3 alkoxy group, a C1-C3 fluorinated alkyl group, a C1-C3 fluorinated alkoxy group or a fluorine atom. Among these, Y ⁵ is preferably a divalent cyclic group selected from a benzene ring and a cyclohexane ring. Such as an alkyl group mentioned as the heterocyclic and substituted groups include the same ones as mentioned in the foregoing Y ^4.

Wherein [Z1], n represents an integer of 0 to 4, when n is 2 or more, Y ⁵ together may be be the same group or different groups. Among them, n is preferably 1 to 3, and more preferably 2 to 3, from the viewpoint of availability of raw materials and ease of synthesis.

In the formula [Z1], Y ⁶ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms. Represents a group.
Among them, Y ⁶ may be an alkyl group having 1 to 18 carbon atoms, an alkyl fluoride group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a fluoroalkoxy group having 1 to 10 carbon atoms. preferable. More preferably, Y ⁶ is an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms. Particularly preferably, Y ⁶ is an alkyl group having 1 to 9 carbon atoms and an alkoxy group having 1 to 9 carbon atoms.
When Y ⁴ is a divalent organic group having a steroid skeleton, Y ⁶ is preferably a hydrogen atom.

  The alkylene group, alkyl group, fluorinated alkyl group, alkoxy group and fluorine-containing alkoxy group mentioned in the definition in the above formula [Z1] may be any of linear, branched, or cyclic, or a combination thereof. Is also good.

  Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2 , 2-Dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group , 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n -Butyl group, 2,3-dimethyl-n-butyl Group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2 -Trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n-heptyl group, 1-methyl-n-hexyl group, 2- Methyl-n-hexyl group, 3-methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pentyl group, 1,3-dimethyl-n-pentyl group, 2 2,2-dimethyl-n-pentyl group, 2,3-dimethyl-n-pentyl group, 3,3-dimethyl-n-pentyl group, 1-ethyl-n-pentyl group, 2-ethyl-n-pentyl group, 3-ethyl-n-pentyl group, 1-methyl-1-ethyl-n Butyl group, 1-methyl-2-ethyl-n-butyl group, 1-ethyl-2-methyl-n-butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-3-methyl- n-butyl group, n-octyl group, 1-methyl-n-heptyl group, 2-methyl-n-heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n-hexyl group, 1, 2-dimethyl-n-hexyl group, 1,3-dimethyl-n-hexyl group, 2,2-dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n- Hexyl group, 1-ethyl-n-hexyl group, 2-ethyl-n-hexyl group, 3-ethyl-n-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1-methyl-2-ethyl -N-pentyl group, 1-methyl-3-ethyl-n-pentyl Group, 2-methyl-2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n-decyl group , N-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group and the like.

  Examples of the alkoxy group having 1 to 18 carbon atoms include groups in which an oxygen atom (-O-) is bonded to the above alkyl group having 1 to 18 carbon atoms. Specific examples thereof include methoxy, ethoxy, n-propoxy, i-propoxy, c-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, c-butoxy, n-pentoxy, c-pentoxy, Examples include n-hexoxy, n-decyloxy, n-pentadecyloxy, and n-octadecyloxy groups.

  Examples of the fluorinated alkyl group having 1 to 18 carbon atoms include groups in which at least one hydrogen atom in the above alkyl group has been substituted with a fluorine atom. Specific examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, heptafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,3,3-tetrafluoropropyl, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl, nonafluorobutyl, 4,4,4-trifluorobutyl, undecafluoropentyl, 2,2 , 3,3,4,4,5,5,5-nonafluoropentyl, 2,2,3,3,4,4,5,5-octafluoropentyl, tridecafluorohexyl, 2,2,3 3,4,4,5,5,6,6,6-undecafluorohexyl, 2,2,3,3,4,4,5,5,6,6-decafluorohexyl, 3,3,4 , 4,5 , 6,6,6-nonafluorohexyl, and the like.

  Examples of the fluorinated alkoxy group having 1 to 18 carbon atoms include groups in which an oxygen atom (—O—) is bonded to the fluorinated alkyl group having 1 to 18 carbon atoms. Specific examples thereof include fluoromethoxy, difluoromethoxy, trifluoromethoxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, heptafluoropropoxy, 2,2,3,3,3-pentafluoropropoxy, 2,3,3-tetrafluoropropoxy, 2,2,2-trifluoro-1- (trifluoromethyl) ethoxy, nonafluorobutoxy, 4,4,4-trifluorobutoxy, undecafluoropentyloxy, 2, 2,3,3,4,4,5,5,5-nonafluoropentyloxy, 2,2,3,3,4,4,5,5-octafluoropentyloxy, tridecafluorohexyloxy, 2, 2,3,3,4,4,5,5,6,6,6-undecafluorohexyloxy, 2,2,3,3,4,4,5,5 6,6-deca fluoro-hexyloxy, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, and the like.

The alkylene group in Y ² and Y ^3, and the substituent on the cyclic group or the alkyl group in Y ^6, an alkyl fluoride group, an alkoxy group and a fluorine-containing alkoxy group are linear, branched, or cyclic. Any one or a combination thereof may be used.
Further, the alkylene group in Y ² and Y ^3, and the alkyl group, the fluorinated alkyl group, the alkoxy group and the fluorine-containing alkoxy group in Y ⁶ are interrupted by 1 to 3 bonding groups unless the bonding groups are adjacent to each other. May be.

Further, Y ² , Y ⁴ or Y ⁵ represents a divalent cyclic group, Y ⁴ represents a divalent organic group having a steroid skeleton, or Y ² represents —CH ₂ —CH (OH) —. When CH ₂ — represents, or Y ² or Y ³ represents an alkylene group, or Y ⁶ represents an alkyl group or a fluorinated alkyl group, the divalent cyclic group, the divalent having the steroid skeleton organic group, the _{-CH 2 -CH (OH) -CH 2} -, the alkylene group, the alkyl group and the fluorinated alkyl group may be bonded through a bonding group and groups adjacent to them.
The above linking _{group, -O -, - CH 2 O} -, - COO -, - OCO -, - NHCO -, - NHCO-O- and -NH-CO-NH- group selected from the group consisting of Represents

A single bond represented by Y ^{2 to} Y ^6, an alkylene group having 1 to 15 carbon atoms, a benzene ring, a cyclohexane ring, a heterocyclic ring, a divalent organic group having a steroid skeleton, —CH ₂ —CH (OH ) —CH ₂ —, the total number of carbon atoms of an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a fluorinated alkoxy group having 1 to 18 carbon atoms Is 6 to 30, for example, 6 to 20.
Among these, in consideration of properties such as releasability, the above Z ¹ is preferably a group containing an alkyl group having 7 to 18 carbon atoms, and is preferably a group containing an alkyl group having 8 to 15 carbon atoms. More preferred.

Preferred embodiments of the above Z ¹ include, for example, hydrocarbon groups having about 6 to 20 carbon atoms. As a C6-C20 hydrocarbon group, a C6-C20 hydrocarbon group containing a linear, branched or cyclic C6-C20 alkyl group or aromatic group is mentioned.

More preferred embodiments of the above Z ^1, for example, the above-mentioned Y ^1, Y ² and Y ⁴ is single bond, Y ³ is a single bond or an alkylene group having 1 to 15 carbon atoms, n is 0, Y ⁶ is an alkyl group having 1 to 18 carbon atoms, and an alkyl group in which the total number of carbon atoms of Y ³ and Y ⁶ is 6 to 20 is exemplified. Examples of such an alkyl group include, among the above-described alkyl groups, an alkyl group (a-1) having a total of 6 to 20 carbon atoms.

As another preferred embodiment of Z ¹ , for example, Y ^{1 to} Y ⁴ are a single bond, n is 2 to 3, and Y ⁵ is a divalent cyclic group selected from a benzene ring and a cyclohexane ring. And a group (a-2) in which Y ⁶ is an alkyl group having 1 to 18 carbon atoms. Examples of such a group (a-2) include groups represented by the following formulas (a-2-1) to (a-2-7).

（式中、Ｙ⁶は、炭素数１〜１８のアルキル基である。）

(In the formula, Y ⁶ is an alkyl group having 1 to 18 carbon atoms.)

Yet another preferred embodiment of the above Z ^1, for example, the Y ¹ to Y ³ is a single bond, Y ⁴ is a divalent organic group having a steroid skeleton a 17-30 carbon atoms, n Is 0 and Y ⁶ is a hydrogen atom (a-3). Examples of such a group (a-3) include groups represented by the following formulas (a-3-1) to (a-3-8).

（式中、＊は結合位置を表す。）

(In the formula, * represents a bonding position.)

As the Z ¹ , a group represented by the following formula [Z2] is particularly preferable from the viewpoint of peelability.

In the formula, Y ¹ represents a single bond, —O— or —NH—, Y ⁵ represents a divalent cyclic group selected from the group consisting of a benzene ring and a cyclohexane ring, and n is an integer of 1 to 3. And when n is 2 or more, Y ⁵ may be the same or different, and Y ⁶ represents an alkyl group having 1 to 18 carbon atoms.

Further, as Z ¹ , groups represented by the following formulas [Z3], [Z4] and [Z5] are particularly preferable.

In the formula, each of Y ⁶ independently represents an alkyl group having 1 to 18 carbon atoms.

  As described above, the polyamic acid represented by the above formula (1) can be obtained by reacting a diamine component containing a diamine having a specific structure with a tetracarboxylic dianhydride component. Hereinafter, the diamine component and the tetracarboxylic dianhydride component that can be used for synthesizing the polyamic acid used in the present invention will be described in detail.

  Examples of the diamine that can be used for the synthesis of the polyamic acid include diamines represented by the following formula (B1), and diamines represented by the following formulas (B1-1) and (B1-2) are preferable. In the present invention, a diamine represented by the formula (B1-2) that enables peeling with a weaker force is more preferable.

（式中、Ｚ¹は上記と同じ。）

(In the formula, Z ¹ is the same as above.)

（式中、Ｚ¹は上記と同じ。）

(In the formula, Z ¹ is the same as above.)

  Particularly preferred specific examples are 1,3-diamino-4- [4- (trans-4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene, 1- (trans-4-normalheptylcyclohexyl) -2. , 4-Diaminobenzene, 1- (trans-4-normal heptylcyclohexyl) -3,5-diaminobenzene, 1,3-diamino-4- {4- [trans-4- (trans-4-n-pentylcyclohexyl) ) Cyclohexyl] phenoxy} benzene, 1,3-diamino-4- {4- [4- (trans-4-n-pentylcyclohexyl) phenyl] phenoxy} benzene and the like.

In the formula (1), as described above, X ¹ is a phenyl group or a biphenyl group.

The phenyl group and biphenyl group that X ¹ can take can be synthesized by using the following aromatic tetracarboxylic dianhydride when synthesizing the polyamic acid used in the present invention.
That is, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride and the like can be mentioned.

  Among them, aromatic tetracarboxylic dianhydrides represented by any of the following formulas (C1) to (C6) are preferable from the viewpoint of improving the function of the obtained film as a release layer, and the following formulas (C1) to (C1) The aromatic tetracarboxylic dianhydride represented by any of C5) is more preferable.

  The weight average molecular weight of the polyamic acid having a monomer unit represented by the formula (1) used in the present invention needs to be 5,000 or more, preferably 15,000 or more, more preferably 20,000 or more. More preferably, it is 30,000 or more. On the other hand, the upper limit of the weight average molecular weight of the polyamic acid used in the present invention is usually 2,000,000 or less, but it is possible to prevent the viscosity of the resin composition from becoming excessively high and to provide a resin film having high flexibility. In consideration of obtaining reproducibility with good reproducibility, it is preferably 1,000,000 or less, more preferably 200,000 or less.

  The polyamic acid used in the present invention contains the monomer unit represented by the formula (1) in an amount of 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, further more preferably 80 mol% or more. Preferably, the content is 90 mol% or more. By using a polyamic acid having such a monomer unit content, a resin thin film having characteristics suitable for a release film can be obtained with good reproducibility.

  According to a preferred embodiment of the present invention, the polyamic acid contained in the composition for forming a release layer of the present invention is a polymer composed of only a monomer unit represented by the formula (1), that is, a monomer represented by the formula (1) It is a polymer containing 100 mol% of units. At this time, the monomer unit in such a polyamic acid may be only one specific type or two or more types as long as it is represented by the formula (1). In the latter case, the number of the monomer units of the formula (1) contained in the polyamic acid is preferably 2 to 4, more preferably 2 to 3.

  The polyamic acid used in the present invention may contain other monomer units in addition to the monomer units represented by the formula (1). The content of such other monomer units must be less than 50 mol%, preferably less than 40 mol%, more preferably less than 30 mol%, and less than 20 mol%. Is still more preferred, and even more preferably less than 10 mol%.

  Such other monomer units include, for example, a monomer unit of the formula (2).

In the formula (2), X ² represents a tetravalent organic group derived from tetracarboxylic dianhydride, Ya represents ^a divalent organic group derived from diamine, and n represents a natural number.

  Examples of the diamine providing such another monomer unit include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-methyl-1,4-phenylenediamine, 5-methyl-1,3-phenylenediamine, 4-methyl-1,3-phenylenediamine, 2- (trifluoromethyl) -1,4-phenylenediamine, 2- (trifluoromethyl) -1,3-phenylenediamine and 4- (trifluoromethyl) -1 , 3-Phenylenediamine, benzidine, 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 2,3'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) benzidine, 3,3'- Bis (trifluoromethyl) benzidine, 2,3′-bis (trifluoromethyl) benzidine, 4,4 -Diphenyl ether, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-diaminobenzanilide, 5-amino-2- (3-aminophenyl) -1H-benzimidazole, 9,9-bis ( Diamines such as 4-aminophenyl) fluorene are exemplified.

Examples of the tetracarboxylic dianhydride include pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3,3 ', 4,4'-diphenylethertetracarboxylic acid, 3,3', 4,4'-diphenylsulfonetetracarboxylic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid And their dianhydrides and derivatives thereof, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid Acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexyl Tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid, 2,3,5-tricarboxy-2-cyclopentaneacetic acid, bicyclo [ 2.2.2] Oct-7-ene-2,3,5,6-tetracarboxylic acid, 2,3,4,5-tetrahydrofurantetracarboxylic acid, 3,5,6-tricarboxy-2-norbornaneacetic acid , Alicyclic tetracarboxylic acids such as dianhydrides and derivatives thereof, and aliphatic tetracarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid, dianhydrides and derivatives thereof, etc. Can be mentioned. Further, as the above-mentioned tetracarboxylic acid component having an organic group having fluorine, 2,2-bis (3,4-dicarboxyphenyl) hexafluoroisopropylidene having a trifluoromethyl group or a hexafluoroisopropylidene group may be used. , 4,4'-Hexafluoroisopropylidene diphthalic acid, dianhydrides and derivatives thereof, and the like, but are not limited to these compounds.
Further, as the tetracarboxylic acid component, one or more compounds can be used in combination from tetracarboxylic acids and derivatives thereof.

  According to a preferred embodiment of the present invention, the polyamic acid used in the present invention is obtained by reacting an aromatic tetracarboxylic dianhydride as an acid dianhydride with a diamine component containing a diamine represented by the formula (B1). Can be obtained by:

  In the above reaction, the charge ratio (molar ratio) of the aromatic tetracarboxylic dianhydride to the diamine component containing the diamine represented by the above formula (B1) is determined by the desired molecular weight of the polyamic acid, the ratio of the monomer units, and the like. Although it can be set appropriately in consideration of the diamine component 1, the acid anhydride component can be usually about 0.7 to 1.3, preferably about 0.8 to 1.2. .

  The organic solvent used in the above-mentioned reaction is not particularly limited as long as it does not adversely affect the reaction, and specific examples thereof include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone. , N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropylamide, 3-propoxy -N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethylpropylamide, 3- tert-butoxy-N, N-dimethylpropylamide, γ-butyrolactone and the like. In addition, you may use an organic solvent individually by 1 type or in combination of 2 or more types.

  In particular, the organic solvent used for the reaction dissolves the above-mentioned diamine, tetracarboxylic dianhydride, dicarboxylic acid, polyamic acid and polyamide well, and therefore, the amide represented by the formula (S1) and the amides represented by the (S2) And at least one selected from amides represented by the formula (S3):

In the formula, R ¹ and R ² independently represent an alkyl group having 1 to 10 carbon atoms. R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. h represents a natural number, preferably 1 to 3, more preferably 1 or 2.

  Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, and n- Examples include a hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group. Among them, an alkyl group having 1 to 3 carbon atoms is preferable, and an alkyl group having 1 or 2 carbon atoms is more preferable.

The reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent to be used, and is usually about 0 to 100 ° C., but the imidization of the resulting polyamic acid is prevented to maintain a high content of the polyamic acid unit. For this purpose, the temperature is preferably about 0 to 70 ° C., more preferably about 0 to 60 ° C., and still more preferably about 0 to 50 ° C.
The reaction time cannot be unconditionally defined because it depends on the reaction temperature and the reactivity of the raw materials, but is usually about 1 to 100 hours.

  By the method described above, a reaction solution containing the desired polyamic acid can be obtained.

In the present invention, usually, a solution obtained by filtering the reaction solution and then filtering or diluting or concentrating the filtrate can be used as the composition for forming a release layer of the present invention. By doing so, it is possible not only to reduce the incorporation of impurities that may cause the deterioration of the adhesion and the releasability of the obtained release layer, but also to obtain a release layer-forming composition efficiently.
The solvent used for dilution or concentration is not particularly limited, and examples thereof include those similar to the specific examples of the reaction solvent for the above reaction, and these may be used alone or in combination of two or more. .

  Among the above specific examples, considering that a resin thin film with high flatness is obtained with good reproducibility, the solvents used are N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, , 3-Dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone and γ-butyrolactone are preferred.

  The concentration of the polyamic acid with respect to the total mass of the composition for forming a release layer is appropriately set in consideration of the thickness of the thin film (release layer) to be produced, the viscosity of the composition, and the like, but is usually 0.5 to 30 mass. %, Preferably about 5 to 25% by mass.

  Further, the viscosity of the composition for forming a release layer is appropriately set in consideration of the thickness of the thin film to be formed, and the like. In particular, it is intended to obtain a resin thin film having a thickness of about 0.05 to 5 μm with good reproducibility. In this case, the temperature is usually about 10 to 10,000 mPa · s at 25 ° C., preferably about 20 to 1,000 mPa · s, and more preferably about 20 to 200 mPa · s. Here, the viscosity can be measured at a temperature of 25 ° C. of the composition using a commercially available liquid viscometer for viscosity measurement, for example, referring to the procedure described in JIS K7117-2. . Preferably, a viscometer of a conical plate type (cone plate type) is used as the viscometer, and the viscosity of the composition is 25 ° C. using a viscometer of the same type and 1 ° 34 ′ × R24 as a standard cone rotor. It can be measured under the condition of ° C. An example of such a rotational viscometer is TVE-25H manufactured by Toki Sangyo Co., Ltd.

  The composition for forming a release layer according to the present invention may have various components in addition to the polyamic acid and the organic solvent. For example, a cross-linking agent (hereinafter, also referred to as a cross-linkable compound) can be exemplified, but not limited thereto.

  Examples of the crosslinkable compound include a compound containing two or more epoxy groups, a melamine derivative, a benzoguanamine derivative, or a glycoluril having a group in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group, or both. And the like, but are not limited thereto.

Hereinafter, specific examples of the crosslinkable compound will be described, but the invention is not limited thereto.
Examples of the compound containing two or more epoxy groups include cyclohexene structures such as Epolide GT-401, Epolide GT-403, Epolide GT-301, Epolide GT-302, Celloxide 2021, and Celloxide 3000 (all manufactured by Daicel Corporation). Epoxy compound having; epicoat 1001, epicoat 1002, epicoat 1003, epicoat 1004, epicoat 1007, epicoat 1009, epicoat 1010, epicoat 828 (all manufactured by Japan Epoxy Resin Co., Ltd. (currently manufactured by Mitsubishi Chemical Corporation, jER (registered trademark)) Bisphenol A type epoxy compound such as series)); Bisphenol F type epoxy compound such as Epicoat 807 (manufactured by Japan Epoxy Resin Co., Ltd.); Epicoat 152, Epicoat 1 Phenol novolak type epoxy compounds such as No. 4 (above, manufactured by Japan Epoxy Resin Co., Ltd. (currently manufactured by Mitsubishi Chemical Corporation, jER (registered trademark) series)), EPPN201, EPPN202 (above, manufactured by Nippon Kayaku Co., Ltd.); ECON -102, ECON-103S, ECON-104S, ECON-1020, ECON-1025, ECON-1027 (all manufactured by Nippon Kayaku Co., Ltd.), Epicoat 180S75 (Japan Epoxy Resin Co., Ltd. (currently manufactured by Mitsubishi Chemical Corporation, jER (registered trademark) series)); naphthalene type epoxy compounds such as V8000-C7 (manufactured by DIC); denacol EX-252 (manufactured by Nagase ChemteX Corporation); CY175, CY177; CY179, Ara Daito CY-182, Araldite CY-192, Araldite CY-184 (all manufactured by BASF), Epicron 200, Epicron 400 (all manufactured by DIC Corporation), Epicoat 871, Epicoat 872 (all manufactured by Japan Epoxy Resin Co., Ltd.) (Currently jER (registered trademark) series manufactured by Mitsubishi Chemical Corporation), alicyclic epoxy compounds such as ED-5661 and ED-5662 (all manufactured by Celanese Coatings Co., Ltd.); Denacol EX-611, Denacol EX -612, Denacol EX-614, Denacol EX-622, Denacol EX-411, Denacol EX-512, Denacol EX-522, Denacol EX-421, Denacol EX-313, Denacol EX-314, Denacol EX-312 (or more) Nagasechem And aliphatic polyglycidyl ether compounds such as those manufactured by Tex Corporation.

  As a melamine derivative, benzoguanamine derivative or glycoluril having a group in which a hydrogen atom of an amino group is substituted by a methylol group, an alkoxymethyl group or both, an average of 3.7 methoxymethyl groups are substituted per triazine ring. MX-750, MW-30 having an average of 5.8 methoxymethyl groups per triazine ring (manufactured by Sanwa Chemical Co., Ltd.); Cymel 300, Cymel 301, Cymel 303, Cymel 350; Methoxymethylated melamine such as Cymel 370, Cymel 771, Cymel 325, Cymel 327, Cymel 703, Cymel 712, etc .; Methoxymethylated butoxymethylated mesylate such as Cymel 235, Cymel 236, Cymel 238, Cymel 212, Cymel 253, Cymel 254, etc. Min; butoxymethylated melamine such as Cymel 506 and Cymel 508; carboxy group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141; methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1123; Methoxymethylated benzoguanamine such as Cymel 1128; carboxy-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80; butoxymethylated glycoluril such as Cymel 1170; Cymel 1172 Methylolated glycoluril (above, manufactured by Mitsui Cyanamid Co., Ltd. (currently: Nippon Cytec Industries Co., Ltd.), etc. .

  The above-described composition for forming a release layer of the present invention is applied to a substrate and heated to form a thin film (release layer) made of polyimide having high heat resistance, appropriate flexibility, and appropriate linear expansion coefficient. Can be obtained.

  Examples of the substrate (substrate) include glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetylcellulose, ABS, AS, norbornene-based resin, etc.), metal (silicon wafer, etc.), Examples include wood, paper, and slate, and those containing glass or a silicon wafer are preferable. In particular, glass is more preferable since the release layer obtained from the composition for forming a release layer according to the present invention has sufficient adhesion to the release layer. The substrate surface may be made of a single material, or may be made of two or more materials. As an aspect in which the substrate surface is composed of two or more materials, a certain area of the substrate surface is composed of a certain material, and the remaining surface is composed of another material. There is a mode in which a material in a pattern such as a line and space pattern is present in another material.

  The coating method is not particularly limited, and examples thereof include a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, an inkjet method, and a printing method (topographic printing plate). , Intaglio, lithographic, screen printing, etc.).

  Further, as a method for imidizing the polyamic acid contained in the composition for forming a release layer of the present invention, thermal imidization in which the composition applied on the substrate is directly heated, and heating by adding a catalyst to the composition. Catalytic imidization.

  The catalyst imidization of the polyamic acid is carried out by adding a catalyst to the composition for forming a release layer of the present invention, preparing a catalyst-added composition by stirring, applying the composition to a substrate, and heating the resin thin film (release layer). ) Is obtained. The amount of the catalyst is 0.1 to 30 times, preferably 1 to 20 times, the mole of the amic acid group. Also, acetic anhydride or the like can be added as a dehydrating agent to the catalyst-added composition, and the amount thereof is 1 to 50 mol times, preferably 3 to 30 mol times of the amic acid group.

  It is preferable to use a tertiary amine as the imidation catalyst. As the tertiary amine, pyridine, substituted pyridines, imidazole, substituted imidazoles, picoline, quinoline, isoquinoline and the like are preferable.

  The heating temperature at the time of thermal imidization and catalytic imidization is appropriately determined usually within a range of 50 to 550 ° C, but is preferably 200 ° C or higher, and more preferably 450 ° C or lower. By setting the heating temperature in this manner, the imidization reaction can sufficiently proceed while preventing the obtained film from becoming brittle. The heating time cannot be specified unconditionally because it varies depending on the heating temperature, but is usually 5 minutes to 5 hours. Further, the imidation ratio may be in the range of 50 to 100%.

  As a preferred example of the heating mode in the present invention, in consideration of the heat resistance of the obtained resin thin film and the versatility of the apparatus used, the applied composition is heated at 50 to 150 ° C. for 5 minutes to 2 hours, and then stepwise as it is. And finally heating at 200 to 300 ° C. for 30 minutes to 2 hours. In particular, it is preferable to heat at 80 to 120 ° C for 5 to 30 minutes, and then at 230 to 300 ° C for 30 minutes to 1 hour.

  Examples of instruments used for heating include a hot plate and an oven. The heating atmosphere may be under air or under an inert gas, and may be under normal pressure or under reduced pressure.

  The thickness of the release layer is generally about 0.01 to 10 μm, preferably about 0.05 to 5 μm, and the thickness of the coating film before heating is adjusted to realize a resin thin film having a desired thickness.

  The release layer described above has excellent adhesion to a substrate, particularly a glass substrate, and has appropriate adhesion to a resin substrate and appropriate release properties. Therefore, the release layer according to the present invention, in the manufacturing process of the flexible electronic device, without damaging the resin substrate of the device, the resin substrate together with the circuit and the like formed on the resin substrate from the base It can be suitably used for peeling.

Hereinafter, an example of a method for manufacturing a flexible electronic device using the release layer of the present invention will be described.
Using the composition for forming a release layer according to the present invention, a release layer is formed on a glass substrate by the method described above. On this release layer, a resin solution for forming a resin substrate is applied, and by heating this coating film, a resin substrate fixed to a glass substrate is formed via the release layer according to the present invention. . At this time, the resin substrate is formed so as to cover the entire release layer and to have an area larger than the area of the release layer. Examples of the resin substrate include a resin substrate made of a typical polyimide resin or acrylic resin as a resin substrate of a flexible electronic device, and a resin solution for forming the resin substrate includes a polyimide solution, a polyamic acid solution, and an acrylic polymer. Solution. The method for forming the resin substrate may be a conventional method.

  Next, a desired circuit is formed on the resin substrate fixed to the base via the release layer according to the present invention, and then, for example, the resin substrate is cut along the release layer. Is separated from the release layer to separate the resin substrate and the base. At this time, a part of the base may be cut together with the release layer.

In this case, the object to be peeled may be a single layer or a plurality of layers. In order to fabricate various devices, it is realistic to have multiple layers.
The layer (usually a resin substrate) immediately above the release layer among the layers to be peeled depends on the release layer to be used, but has good releasability from the release layer, in other words, adherence to the release layer to be used. It is better to use one with poor properties.

In addition, the present invention provides the following method for producing an object to be peeled.
A step of applying the release layer-forming composition of the present invention on a substrate and baking to form a release layer,
Provided is a method for manufacturing an object to be peeled, the method including a step of forming an object to be peeled on the peeling layer, and a step of peeling the object to be peeled from the peeling layer.

In the above manufacturing method, the above-described conditions can be adopted as the firing conditions for forming the release layer.
The “peeled object” may be a single layer or a plurality of layers. The layer (usually, a resin substrate) immediately above the release layer in the “peeled object” depends on the release layer to be used, but has good releasability from the release layer, in other words, a layer with the release layer to be used. It is preferable that the adhesiveness is not good.

Further, the present invention is a laminate applied to a flexible electronic device,
A substrate;
A release layer formed on the substrate,
A resin substrate formed on the release layer, wherein the release layer is formed of the composition for forming a release layer of the present invention, and the adhesion between the resin substrate and the release layer is the release layer And a laminate having a greater adhesion to the substrate.
It should be noted that the magnitude of the adhesion can be confirmed by, for example, a cross-cut test shown in Examples described later.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to these Examples.
[1] Abbreviation of compound NMP: N-methylpyrrolidone BCS: butyl cellosolve PGME: propylene glycol monomethyl ether TFMB: 2,2′-bis (trifluoromethyl) benzidine PCH7AB: 1- (trans-4-normal heptylcyclohexyl) -2 , 4-Diaminobenzene m-PCH7AB: 1- (trans-4-normal heptylcyclohexyl) -3,5-diaminobenzene PBCH5DAB: 1,3-diamino-4- {4- [trans-4- (trans-4- n-pentylcyclohexyl) cyclohexyl] phenoxy} benzene BPTP: bis (4-aminophenoxy) terephthalate CBDA: cyclobutanoic dianhydride PMDA: pyromellitic dianhydride BODAxx: bicyclo [2.2.2] oct-2- exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid-2,3: 5,6-dianhydride

[2] Measurement of Weight Average Molecular Weight and Molecular Weight Distribution The weight average molecular weight (hereinafter abbreviated as Mw) and the molecular weight distribution of the polymer were eluted using a GPC apparatus (column: Shodex (registered trademark) KF803L and KF805L) manufactured by JASCO Corporation. Dimethylformamide was measured as a solvent at a flow rate of 1 mL / min and a column temperature of 50 ° C. Note that Mw was a value in terms of polystyrene.

[3] Synthesis of polymer <Synthesis example S1 Synthesis of polyimide (S1) for film>
In a 250 mL reaction three-necked flask equipped with a nitrogen inlet / outlet, a mechanical stirrer, and a condenser, 25.61 g (0.08 mol) of TFMB was placed. Thereafter, 173.86 g of γ-butyrolactone was added, and stirring was started. Immediately after TFMB was completely dissolved in the solvent, 10 g (0.04 mol) of stirred BODAxx, 7.84 g (0.04 mol) of CBDA and 43.4 g of γ-butyrolactone were added and heated to 140 ° C. under nitrogen. did. Thereafter, 0.348 g of 1-ethylpiperidine was added to the solution and heated to 180 ° C. under nitrogen for 7 hours. Finally, heating was stopped, the reaction solution was diluted to 10% and stirring was maintained overnight. The polyimide reaction solution was added to 2,000 g of methanol and stirred for 30 minutes, and then the polyimide was purified by filtering the polyimide solid.Then, the polyimide solid was stirred in 2,000 g of methanol for 30 minutes to remove the polyimide solid. Filtered. This purification procedure of stirring and filtration of the polyimide solid was repeated three times. The methanol residue in the polyimide was removed by drying in a vacuum oven at 150 ° C. for 8 hours to finally obtain 31.16 g of dried polyimide S1, with a weight percent yield of the polyimide S1 of 74% ( Mw = 169,802, Mn = 55,308).

<Synthesis Example L1 Synthesis of polyamic acid (L1)>
After dissolving 4.022 g (9.253 mmol) of PBCH5DAB in 44 g of NMP and adding 1.977 g (9.068 mmol) of PMDA, the mixture was reacted at 23 ° C. for 2 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 10,400 and the molecular weight distribution was 1.89.

<Synthesis Example L2 Synthesis of polyamic acid (L2)>
After dissolving 3.842 g (10.10 mmol) of m-PCH7AB in 44 g of NMP and adding 2.158 g (9.8934 mmol) of PMDA, the mixture was reacted at 23 ° C. for 2 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 173,900 and the molecular weight distribution was 4.19.

<Synthesis Example L3 Synthesis of polyamic acid (L3)>
After dissolving 3.842 g (10.10 mmol) of PCH7AB in 44 g of NMP and adding 2.158 g (9.8934 mmol) of PMDA, the mixture was reacted at 23 ° C. for 2 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 12,100 and the molecular weight distribution was 1.85.

<Synthesis Example L4 Synthesis of polyamic acid (L4)>
1.974 g (5.1883 mmol) of PCH7AB and 1.807 g (5.1883 mmol) of BPTP were dissolved in 44 g of NMP, and 2.218 g (10.17 mmol) of PMDA was added, followed by reaction at 23 ° C. for 2 hours under a nitrogen atmosphere. Was. The Mw of the obtained polymer was 53,700 and the molecular weight distribution was 1.89.

<Comparative Synthesis Example Synthesis of Polyamic Acid (HL1)>
2.86 g (0.0089 mol) of TFMB was dissolved in 35.2 g of NMP, and 1.944 g (0.00991 mol) of CBDA was added, followed by a reaction at 23 ° C. for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 69,200 and the molecular weight distribution was 2.2. The resulting solution was soluble in PGME.

[4] Preparation of Composition for Forming Resin Substrate The polyimide S1 obtained in Synthesis Example S1 was dissolved in γ-butyrolactone so as to be 15% by mass, and used as a composition for forming a resin substrate.

[5] Preparation of composition for forming release layer [Example 1-1]
BCS and NMP were added to the reaction solution obtained in Synthesis Example L1, and the mixture was diluted so that the polymer concentration was 5% by mass and the BCS was 20% by mass to obtain a composition L1 for forming a release layer.

[Examples 1-2 to 1-4]
Except that the reaction solutions obtained in Synthesis Examples L2 to L4 were used instead of the reaction solutions obtained in Synthesis Example L1, the compositions L2 to R3 were formed in the same manner as in Example 1-1. L4 was obtained.

[Comparative Example 1-1]
14 g of γ-butyrolactone was added to 20 g of MA-ST sol (silica sol manufactured by Nissan Chemical Industries, Ltd.), and methanol was distilled off under reduced pressure using an evaporator to prepare 20 g of a γ-butyrolactone solution of silica sol. On the other hand, 3 g of the polyimide S1 obtained in Synthesis Example S1 was dissolved in 67 g of a γ-butyrolactone solution to prepare a γ-butyrolactone solution of the polyimide S1. Thereafter, the two solutions were stirred at 23 ° C. for 2 hours to obtain a release layer forming composition HL1.

[6] Production of release layer and resin substrate [Example 2-1]
Using a spin coater (condition: about 30 seconds at a rotation speed of 3,000 rpm), the composition L1 for forming a release layer obtained in Example 1-1 was applied to a 100 mm × 100 mm glass substrate as a glass substrate (the same applies hereinafter). Coated on top.
Then, the obtained coating film is heated at 120 ° C. for 5 minutes using a hot plate, and then heated at 240 ° C. for 60 minutes in the presence of air using an oven. A 1 μm release layer was formed to obtain a glass substrate with a release layer.

  Using a bar coater (gap: 250 μm), the composition for forming a resin substrate was applied onto the release layer (resin thin film) on the glass substrate. Then, the obtained coating film was heated at 120 ° C. for 10 minutes using a hot plate, and then heated at 250 ° C. for 60 minutes in the presence of air using an oven, and a film having a thickness of about 20 μm was formed on the release layer. A resin substrate was formed to obtain a resin substrate and a glass substrate with a release layer.

[Examples 2-2 to 2-4]
In place of the release layer forming composition L1 obtained in Example 1-1, the release layer forming compositions L2 to L4 obtained in Examples 1-2 to 1-4 were used, respectively. A release layer and a resin substrate were formed in the same manner as in Example 2-1 to prepare a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer.

[Comparative Example 2-1]
The same as Example 2-1 except that the composition for forming a release layer HL1 obtained in Comparative Example 1-1 was used instead of the composition for forming a release layer L1 obtained in Example 1-1. A release layer and a resin substrate were formed by the method, and a glass substrate with a release layer and a glass substrate with a resin substrate and a release layer were produced.

[7] Evaluation of Peelability For the glass substrates with a release layer obtained in Examples 2-1 to 2-4 and Comparative Example 2-1 described above, the releasability between the release layer and the glass substrate was measured using a resin substrate and a release layer. With respect to the attached glass substrate, the releasability between the release layer and the resin substrate was confirmed by the following method.
<Evaluation of cross-cut test peelability of resin thin film>
The release layer on the glass substrate provided with a release layer obtained in Examples 2-1 to 2-4 and Comparative Example 2-1 was cross-cut (1 mm vertically and horizontally, the same applies hereinafter), and 100 mask cuts were performed. That is, 100 cross sections of 1 mm square were formed by this cross cutting.
Then, an adhesive tape was attached to the 100 muscat portions, the tape was peeled off, and the degree of peeling was evaluated based on the following criteria (5B to 0B, B, A, AA). Table 1 shows the results.
<Judgment criteria>
5B: 0% peeling (no peeling)
4B: less than 5% peel 3B: less than 5-15% peel 2B: less than 15-35% peel 1B: less than 35-65% peel 0B: 65% -less than 80% peel B: 80% -95 % Peeling A: 95% to less than 100% peeling AA: 100% peeling (all peeling)

<Evaluation of initial peeling force of resin substrate>
The resin substrate of the resin substrate and the glass substrate with the release layer obtained in Examples 2-1 to 2-4 and Comparative Example 2-1 was cut into a 25 mm-wide strip using a cutter. Then, a cellophane tape was stuck to the tip of the cut resin substrate, and this was used as a test piece. The test piece was subjected to a peel test using a push-pull tester manufactured by Atonic Co., Ltd. so that the peel angle was 90 °, and the peel force was measured based on the following criteria (5B to 0B, B, A, AA). evaluated. Table 1 shows the results.
<Judgment criteria>
5B: 0% peeling (no peeling)
4B: less than 5% peel 3B: less than 5-15% peel 2B: less than 15-35% peel 1B: less than 35-65% peel 0B: 65% -less than 80% peel B: 80% -95 % Peeling A: 95% to less than 100% peeling AA: 100% peeling (all peeling)

As shown in Table 1, it was confirmed that the release layers of Examples 2-1 to 2-4 had excellent adhesion to the glass substrate and also excellent release to the resin substrate.
On the other hand, it was confirmed that the release layer of Comparative Example 2-1 was excellent in adhesion to the glass substrate, but was inferior to release from the resin substrate.

Claims (11)

A composition for forming a release layer, comprising a polyamic acid having a weight average molecular weight of 5,000 or more containing a structural unit represented by the following formula (1) and an organic solvent.

[Wherein, X ¹ represents a phenyl group or a biphenyl group, Z ¹ is a group represented by the following formula [Z1], and n ¹ represents a natural number.)

(In the formula [Z1],
Y ¹ represents a single bond or a bonding group,
Y ² represents a single bond, an alkylene group having 1 to 15 carbon atoms or —CH ₂ —CH (OH) —CH ₂ —, or a divalent group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. Represents a cyclic group, and any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, May be substituted with a fluorinated alkoxy group or a fluorine atom,
Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms,
Y ⁴ represents a single bond or a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a steroid skeleton having 17 to 30 carbon atoms, Any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxy group having 1 to 3 carbon atoms Or may be substituted with a fluorine atom,
Y ⁵ represents a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, May be substituted with an alkoxy group having 1 to 3, a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxy group having 1 to 3 carbon atoms or a fluorine atom,
n represents an integer of 0 to 4, when n is 2 or more, Y ⁵ together may be the same or different,
Y ⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorinated alkoxy group having 1 to 18 carbon atoms,
The alkylene group in Y ² and Y ^3, and the substituent on the cyclic group or the alkyl group, fluorinated alkyl group, alkoxy group and fluorine-containing alkoxy group in Y ⁶ may be any of linear, branched, or cyclic. Or a combination thereof,
The alkylene group in Y ² and Y ³ and the alkyl group, fluorinated alkyl group, alkoxy group and fluorine-containing alkoxy group in Y ⁶ are interrupted by 1 to 3 bonding groups unless the bonding groups are adjacent to each other. May be
Further, Y ² , Y ⁴ or Y ⁵ represents a divalent cyclic group, Y ⁴ represents a divalent organic group having a steroid skeleton, or Y ² represents —CH ₂ —CH (OH) —CH _{When 2-} represents, or Y ² or Y ³ represents an alkylene group, or Y ⁶ represents an alkyl group or a fluorinated alkyl group, the divalent cyclic group or the divalent organic having the steroid skeleton group, the _{-CH 2 -CH (OH) -CH 2} -, the alkylene group, the alkyl group and the fluorinated alkyl group may be bonded through a bonding group and groups adjacent to them,
The bonding group is a group consisting of —O—, —CH ₂ O—, —COO—, —OCO—, —NH—, —NHCO—, —NH—CO—O—, and —NH—CO—NH—. Represents a group selected from
However, a single bond represented by each of Y ^{2 to} Y ^6, an alkylene group having 1 to 15 carbon atoms, a benzene ring, a cyclohexane ring, a heterocyclic ring, a divalent organic group having a steroid skeleton, —CH ₂ —CH (OH ) —CH ₂ —, the total number of carbon atoms of an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a fluorinated alkoxy group having 1 to 18 carbon atoms Is 6 to 30. )] 2. The composition for forming a release layer according to claim 1, wherein Z ¹ is a group represented by the following formula [Z2]. 3.

(Wherein, Y ¹ represents a single bond, —O— or —NH—,
Y ⁵ represents a divalent cyclic group selected from the group consisting of a benzene ring and a cyclohexane ring,
n represents an integer of 1 to 3, when n is 2 or more, Y ⁵ together may be the same or different,
Y ⁶ represents an alkyl group having 1 to 18 carbon atoms. ) It said Z ¹ is a compound represented by the following formula [Z3], [Z4] or [Z5] is a group represented by the claims 2 peel layer forming composition.

(In the formula, Y ⁶ independently represents an alkyl group having 1 to 18 carbon atoms.) The said organic solvent contains at least one selected from the amide represented by Formula (S1), the amide represented by Formula (S2), and the amide represented by Formula (S3). The composition for forming a release layer according to any one of the above.

(Wherein, R ¹ and R ² independently represent an alkyl group having 1 to 10 carbon atoms, R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and h is a natural number. Represents.)   A release layer formed using the composition for forming a release layer according to claim 1.   A method for producing a release layer, comprising applying the composition for forming a release layer according to any one of claims 1 to 4 onto a substrate and firing the composition. A step of applying the composition for forming a release layer according to any one of claims 1 to 4 on a substrate and baking to form a release layer,
A method for manufacturing a body to be peeled, the method including a step of forming a body to be peeled over the peeling layer, and a step of peeling the body to be peeled from the peeling layer.   A method for manufacturing a flexible electronic device comprising a resin substrate, comprising using the release layer according to claim 5.   A method for manufacturing a touch panel sensor having a resin substrate, comprising using the release layer according to claim 5.   9. The method according to claim 7, wherein the resin substrate is a polyimide resin substrate. A laminate applied to a flexible electronic device,
A substrate;
A release layer formed on the substrate,
A resin substrate formed on the release layer, wherein the release layer is formed of the composition for forming a release layer according to any one of claims 1 to 4, and the resin substrate and the release layer Characterized in that the adhesion between the substrate and the substrate is greater than the adhesion between the release layer and the substrate.